US11456493B2 - Method for precisely analyzing degree of impregnation of electrolyte of electrode in cell - Google Patents
Method for precisely analyzing degree of impregnation of electrolyte of electrode in cell Download PDFInfo
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- US11456493B2 US11456493B2 US16/771,146 US201916771146A US11456493B2 US 11456493 B2 US11456493 B2 US 11456493B2 US 201916771146 A US201916771146 A US 201916771146A US 11456493 B2 US11456493 B2 US 11456493B2
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/3644—Constructional arrangements
- G01R31/3648—Constructional arrangements comprising digital calculation means, e.g. for performing an algorithm
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- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
- G01R31/3842—Arrangements for monitoring battery or accumulator variables, e.g. SoC combining voltage and current measurements
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for precisely analyzing the degree of electrolyte impregnation of an electrode in a cell to determine at which cycle the electrolyte is sufficiently impregnated through a differential capacity curve which is obtained by differentiating a capacity-voltage profile with respect to the capacity for each charge/discharge cycle.
- secondary batteries capable of charging and discharging have been widely used as energy sources of wireless mobile devices.
- the secondary battery has attracted attention as an energy source of an electric vehicle, a hybrid electric vehicle, etc., which are proposed as a solution for air pollution of existing gasoline vehicles and diesel vehicles using fossil fuel. Therefore, the types of applications using the secondary battery are currently much diversified due to the advantages of the secondary battery, and it is expected that the secondary battery will be applied to many fields and products in the future.
- lithium secondary batteries having a high energy density and working potential, a long cycle life and a low self-discharge rate are commercialized and widely used.
- an electrode assembly is prepared by stacking the positive electrode and negative electrode and the separator alternately coated with the active material, respectively, the electrode assembly is inserted into a battery case made up of cans or pouches of any size and shape, and then the electrolyte is injected to thereby manufacture the lithium secondary battery. At this time, the electrolyte injected later is permeated between the positive electrode, the negative electrode and the separator by a capillary force.
- the electrode plates of lithium secondary batteries have increased in size, while the volume to which the electrolyte can penetrate is reduced, which has increased the possibility that the electrolyte cannot be impregnated to the inside of the battery and is present only locally.
- the performance of the secondary battery may be degraded and the safety of the battery may be lowered.
- the positive electrode, the negative electrode, and the separator are all hydrophobic materials, whereas the electrolyte is a hydrophilic material, so that the time required for electrolyte penetration is relatively increased or the impregnation efficiency is decreased.
- Such poor impregnation of the electrolyte may cause a problem of shortening the life of the battery by accelerating the deterioration of the electrode despite the good state of the other electrode.
- an object of the present invention is to solve the problem of the conventional measurement of the degree of electrolyte impregnation, and is to provide a measuring method for more accurately recognizing at which time point the electrolyte was sufficiently impregnated using the battery cell manufactured with the electrode used as an evaluation object.
- a method for analyzing an electrolyte impregnation degree of an electrode in a battery cell including: a battery cell manufacturing step (S 1 ) of preparing a battery cell by injecting an electrolyte into a battery cell including an electrode to be evaluated; a step (S 2 ) of charging/discharging the battery cell several times and obtaining a capacity-voltage profile for each cycle; a step (S 3 ) of obtaining a differential capacity (dV/dQ) curve generated by differentiating the capacity-voltage profile for each cycle with respect to the capacity; and a step (S 4 ) of determining a cycle, at which a behavior becomes the same, as a time point when the impregnation has been sufficiently performed in the differential capacity curve.
- the battery cell may be one selected from the group consisting of a pouch type, a cylindrical type, a square type and a coin type.
- the battery cell may be a half cell.
- the battery cell may be a full cell.
- the electrode may be a negative electrode.
- the negative electrode may include one or two negative electrode active materials selected from the group consisting of artificial graphite and natural graphite.
- the charge/discharge may be a C-rate condition of 0.1 C to 0.3 C.
- the charge/discharge may be a C-rate condition of 0.15 C to 0.25 C.
- the number of cycles may be 1 to 10.
- the number of cycles may be 3 to 7.
- a battery cell was fabricated with an electrode to be evaluated, and the initial charge and discharge were repeated and the differential capacity curve obtained by differentiating the capacity of the charge/discharge profile at this time was analyzed to thereby making it possible to determine at which time point the electrolyte was sufficiently impregnated.
- FIG. 1 is a flowchart illustrating a method of measuring an electrolyte impregnation degree of an electrode in a battery cell according to one embodiment of the present invention
- FIG. 2 is a graph showing the result of measuring capacity according to charge and discharge cycles of a half cell according to a comparative example
- FIG. 3 is a graph showing differential capacity (dV/dQ) obtained by differentiating a charging profile by capacity for each cycle of a negative electrode coin half cell according to an example of the present invention.
- FIG. 4 is a graph showing the differential capacity (dV/dQ) of three cycles of Example 1 and one cycle of the Reference Example of the present invention.
- FIG. 5 is a graph showing differential capacity (dV/dQ) obtained by differentiating a charging profile by capacity for each cycle of a full cell according to Example 2 of the present invention.
- impregnation degree and “degree of impregnation” refer to the degree to which an electrolyte penetrates into an electrode, particularly an electrode active material, and may be interchanged with the term “wetting”.
- the positive electrode material or the negative electrode material constituting the lithium secondary battery has a crystal structure, and lithium ions are repeatedly inserted and detached into and from the crystal structure according to charge/discharge, which is called intercalation/de-intercalation. Since lithium ions move between the positive electrode and the negative electrode through the electrolyte, if the electrolyte is not sufficiently impregnated with the positive electrode and the negative electrode, all of the reactable lithium ions cannot be intercalated. On the contrary, when the electrolyte is sufficiently impregnated, all of the reactable lithium ions can be intercalated.
- the differential capacity (dV/dQ) graph that is generated by differentiating the charging profile of the lithium secondary battery against the capacity has a plurality of peaks due to the phase transition between the intercalation steps of lithium ions. It has been found that during initial charging, the behavior of the differential capacity (dV/dQ) graph changes by charging cycle, and the behavior of the differential capacity graph (dV/dQ) becomes similar over a certain number of cycles, which are because as charging and discharging are repeated, all reactable lithium ions are intercalated, and the behavior of the differential capacity graph (dV/dQ) due to intercalation converges in a certain form.
- FIG. 1 is a flowchart illustrating a method of measuring an electrolyte impregnation degree of an electrode in a battery cell according to one example of the present invention.
- the method for measuring the electrolyte impregnation degree of the electrode in the battery cell according to the present invention includes: a battery cell manufacturing step (S 1 ) of impregnating the electrode by injecting the electrolyte to the battery cell including the electrode to be evaluated; a step (S 2 ) of charging/discharging the battery cell several times and obtaining a capacity-voltage profile for each cycle; a step (S 3 ) of obtaining a differential capacity (dV/dQ) curve generated by differentiating the capacity-voltage profile for each cycle with respect to the capacity; and a step (S 4 ) of determining a cycle in which the behavior becomes the same as a time when the impregnation has been sufficiently performed in the differential capacity curve.
- the battery cell manufacturing step (S 1 ) of the present invention is a step of preparing a battery cell by injecting an electrolyte into a battery cell including an electrode to be measured about the degree of impregnation of the electrolyte.
- the battery cell manufacturing step (S 1 ) may further include a step of wetting the electrolyte to be impregnated in the electrode. At this time, the wetting time may be 1 hour to 24 hours.
- the method of analyzing the electrolyte impregnation degree of the present invention can be applied to all kinds of secondary batteries such as a cylindrical secondary battery, a pouch type secondary battery, a square secondary battery and a coin-type secondary battery, and a full-cell containing positive electrode and negative electrode as well as a half-cell containing positive electrode or negative electrode and counter electrode.
- secondary batteries such as a cylindrical secondary battery, a pouch type secondary battery, a square secondary battery and a coin-type secondary battery, and a full-cell containing positive electrode and negative electrode as well as a half-cell containing positive electrode or negative electrode and counter electrode.
- the electrode to be evaluated in the battery cell may be a negative electrode.
- the negative electrode may be manufactured by coating a negative electrode mixture including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
- the negative electrode current collector is generally made to a thickness of 3 to 500 micrometers.
- the negative electrode current collector is not particularly limited as long as it has high electrical conductivity without causing chemical changes in the battery, and examples thereof include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel of which the surface has been treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like. Further, fine unevenness may be formed on the surface to enhance the binding force of the negative electrode active material, and it may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- Examples of the negative electrode active material include natural graphite, artificial graphite, carbonaceous material; metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; alloys composed of the metals (Me); oxides of the above metals; and one or two or more negative electrode active materials selected from the group consisting of metals and composites with carbon.
- metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe
- alloys composed of the metals (Me) oxides of the above metals
- one or two or more negative electrode active materials selected from the group consisting of metals and composites with carbon.
- the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt % based on the total weight of the negative electrode mixture.
- binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, various copolymers thereof and the like.
- PVDF polyvinylidene fluoride
- CMC carboxymethylcellulose
- EPDM ethylene-propylene-diene polymer
- EPDM ethylene-propylene-diene polymer
- sulfonated EPDM styrene butadiene rubber
- the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt % based on the total weight of the negative electrode mixture.
- a conductive material is not particularly limited as long as it has electrical conductivity without causing a chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives and the like.
- the solvent may include an organic solvent such as water or NMP (N-methyl-2-pyrrolidone), and may be used in an amount that becomes a desirable viscosity when the negative electrode active material and optionally a binder and a conductive material are included.
- the concentration of the negative electrode active material and, optionally, the solids including the binder and the conductive material may be included in an amount of 50 wt % to 95 wt %, preferably 70 wt % to 90 wt %.
- the battery cell may be a full cell including both a positive electrode and a negative electrode.
- the positive electrode may be manufactured by coating a positive electrode mixture including a positive electrode active material, a binder, a conductive material, and a solvent on a positive electrode current collector, followed by drying and rolling.
- the positive electrode active material may be included in 80% by weight to 99% by weight based on the total weight of each positive electrode mixture.
- the conductive material is usually added in an amount of 1 to 30% by weight based on the total weight of the positive electrode mixture.
- Such a conductive material is not particularly limited as long as it has electrical conductivity without causing a chemical change in the battery, and examples thereof include graphite; a carbonaceous material such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives and the like.
- a carbonaceous material such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
- conductive fibers such as carbon fiber and metal fiber
- metal powders such as carbon fluoride, aluminum and nickel powder
- conductive whiskey such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- conductive materials such as polyphenylene derivatives and the like.
- conductive materials include products of Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company products, Ketjenblack, EC series (Armak Company), Vulcan XC-72 (Cabot Company) and Super P (Timcal).
- the binder is added in an amount of 1 to 30% by weight, on the basis of the total weight of the positive electrode mixture, as a component that assists in bonding between the active material and the conductive material and bonding to the current collector.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
- the solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that becomes a desirable viscosity when the positive electrode active material and optionally a binder and a conductive material are included.
- NMP N-methyl-2-pyrrolidone
- the concentration of the positive electrode active material and, optionally, the solids including the binder and the conductive material may be included in an amount of 50 wt % to 95 wt %, preferably 70 wt % to 90 wt %.
- impregnation or wetting of electrolyte solution in a secondary battery means that a non-aqueous electrolyte solution penetrates between a positive electrode, a negative electrode, and a separator by capillary force. Specifically, the electrolyte penetrates into the electrode active material on the electrode surface.
- the positive electrode, the negative electrode (particularly the positive electrode, the negative electrode active material) and the separator are all hydrophobic (hydrophobicity) material, while in many cases, the impregnation of the electrolyte does not occur quickly (so-called impregnation delay or poor impregnation).
- impregnation delay or poor impregnation when the impregnation of the electrolyte is degraded due to the impregnation delay, the electrolyte does not reach the active material particles of the electrode, the lithium ions are not moved smoothly, and the exhibition of performance of the normal secondary battery is delayed.
- the electrolyte used to manufacture the battery cell of the present invention is commonly used in the production of a lithium secondary battery, and includes a non-aqueous organic solvent and a lithium salt.
- the non-aqueous organic solvent is not particularly limited as long as it can minimize decomposition by an oxidation reaction or the like during charging and discharging of a battery and can exhibit desired properties with additives.
- a carbonate compound or a propionate compound may be used alone, or two or more thereof may be mixed and used.
- Examples of such carbonate compounds include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and vinylene carbonate (VC), or a mixture of two or more thereof.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- DPC dipropyl carbonate
- MPC methylpropyl carbonate
- EPC ethylpropyl carbonate
- MEC methylethyl carbonate
- EC ethylene carbonate
- PC propylene carbonate
- BC butylene carbonate
- VC vinylene carbonate
- propionate-based compound includes any one selected from the group consisting of ethyl propionate (EP), propyl propionate (PP), n-propyl propionate, iso-propyl propionate, n-butyl propionate, iso-butyl propionate and tert-butyl propionate, or a mixture of two or more thereof.
- EP ethyl propionate
- PP propyl propionate
- n-propyl propionate iso-propyl propionate
- n-butyl propionate iso-butyl propionate and tert-butyl propionate
- tert-butyl propionate or a mixture of two or more thereof.
- examples of the non-aqueous organic solvent may include N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxy ethane, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl propionate, and ethyl propionate.
- the lithium salt is a substance that is soluble in the non-aqueous electrolyte.
- the examples of the lithium salt include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LICF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 Nli, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium 4-phenylborate, imide and the like.
- the electrolyte may include vinylene carbonate (VC), propane sulfone (PS), Fluoro-Ethylene Carbonate (FEC), NA, AsA3, etc. for the purpose of improving the charge and discharge characteristics, flame retardancy, etc.
- VC vinylene carbonate
- PS propane sulfone
- FEC Fluoro-Ethylene Carbonate
- NA NA
- AsA3 AsA3, etc.
- the battery cell After fabricating the battery cell (S 1 ), the battery cell is charged/discharged several times, and a step (S 2 ) of obtaining a capacity-voltage profile for each charge/discharge cycle is performed.
- the step of obtaining the capacity-voltage profile is a step of obtaining a voltage profile according to the capacity by measuring the capacity and voltage of the battery cell while flowing a charge/discharge current to the battery cell.
- the charge/discharge is performed at a rate of C-rate of 0.1 C to 0.3 C, preferably 0.15 C to 0.25 C, more preferably 0.18 C to 0.22 C.
- C is the secondary battery capacity of the charging unit Ah
- the current in amperes is selected as the fraction (or multiplier) of C.
- 1 C means the charge/discharge rate of drawing or filling the capacity of a fully charged secondary battery within 1 hour, and also means the current density at that time.
- the charge and discharge rate of the present invention is less than 0.1 C, it is not desirable because excessive time is required for charging and discharging, and when it exceeds 0.3 C, it is not desirable because it can adversely affect the formation of electrolyte interphase such as non-uniform thickness and discontinuity of the layer in the negative electrode.
- the number of charge/discharge cycles may be 1 to 9, preferably 3 to 7, more preferably 4 to 6.
- the x-axis denotes the capacity and the y-axis denotes the voltage.
- the capacity-voltage profile for each cycle can be derived by measuring the voltage according to the charge/discharge capacity in each cycle while performing the charge/discharge of the battery cell including the electrode to be evaluated several times.
- a step (S 3 ) of obtaining a differential capacity (dV/dQ) curve obtained by differentiating the capacity-voltage profile with respect to the capacity is performed.
- the charge profile (x-axis: capacity, y-axis: voltage) of each cycle is differentiated with respect to the capacity, and each cycle charging profile and the capacity of the battery cell may be applied to the following general formula to thereby calculate the differential capacity.
- dV/dQ ( V t ⁇ V t-1 )/( Q t ⁇ Q t-1 ) [Formula 1]
- V t charge/discharge profile of the battery cell at time t
- V t-1 Charge/discharge profile of the battery cell 1 unit time before time t
- step S 4 of determining the cycle in which the behavior becomes the same, as the time point when the impregnation is sufficient, from the differential capacity curve, the behavior observed in the differential capacity graph curve is observed to determine the impregnation degree of the electrolyte.
- the operating principle of the lithium ion battery is that during discharge, lithium is oxidized to lithium ions at the negative electrode and then moves to the positive electrode through the electrolyte, and the generated electrons move to the positive electrode through the external conductor.
- lithium ions moved from the negative electrode are inserted to accept electrons and cause a reduction reaction.
- the oxidation reaction occurs at the positive electrode and the reduction reaction occurs at the negative electrode.
- the phenomenon in which lithium ions are inserted into the crystal structure of positive electrode material or negative electrode material is called intercalation.
- the peak of the differential capacity graph is due to the intercalation step of the electrode.
- the peak represents the phase transition between different intercalation steps according to Gibb's phase rule.
- the intercalation is closely related to the impregnation degree of the electrodes in the electric cell. If the degree of impregnation of the electrolyte of the electrode is not sufficient, lithium ions contained in the electrolyte are not sufficiently intercalated with the electrode, and thus the charge capacity and the discharge capacity are not properly expressed.
- lithium ions of the electrolyte may be sufficiently intercalated during the charging or discharging period in the electrode to thereby sufficiently express the charge capacity and the discharge capacity of the battery cell.
- the charge capacity and the discharge capacity sufficiently expressed as described above are represented by the differential capacity graph curve, the same behavior showing the same peak is shown.
- step (S 4 ) of determining a cycle, in which the behavior becomes the same, as the time point when the impregnation is sufficient, from the differential capacity curve it can be determined, by observing the peak point on the differential capacity curve graph, that the impregnation of the electrode in the electric cell has reached a sufficient level in a cycle in which the behavior of the peak becomes the same. That is, by measuring the peak value of the differential capacity graph for each cycle, it is possible to determine the first cycle, in which the same peak value is repeated, as a time point when the impregnation has been sufficiently performed.
- the behavior of the differential capacity graph (dV/dQ) for each cycle changes during initial charging, and the behavior of the differential capacity graph (dV/dQ) becomes similar for a certain number of cycles, which is because all of the lithium ions that can react with charge and discharge are intercalated, and the behavior of the differential capacity graph (dV/dQ) due to intercalation converges in a certain form.
- NMP N-methyl-2-pyrrolidone
- the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector with a thickness of 20 ⁇ m, and then dried. At this time, the temperature of the air circulated was 80° C. Then, a roll press was carried out and dried in a vacuum oven at 130° C. for 12 hours to prepare a negative electrode.
- Cu copper
- the negative electrode prepared as described above was cut into a circle of 1.4875 cm′ to be used as a negative electrode, and a lithium (Li) metal thin film cut into a circle of 1.7671 cm′ to be used as a counter electrode.
- a separator of porous polyethylene was interposed between the negative electrode and the counter electrode, and 0.5 wt % vinylene carbonate and 1 M LiPF 6 dissolved electrolyte were injected into a mixed solution of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) with a volume ratio of 7:3, to thereby prepare a lithium coin half cell.
- EMC ethyl methyl carbonate
- EC ethylene carbonate
- the battery After storing the half cell of the manufacturing example at room temperature for 3 hours, the battery was charged under 0.1 C c-rate condition, and the charged coin half cell was discharged under 0.1 C c-rate condition in one cycle. And the cycle of charge/discharge was repeated 5 times (voltage range: 0.005 V to 1 V). In addition, the charge capacity and the discharge capacity were measured for each cycle, and the results are shown in FIG. 2 .
- the electrolyte impregnation time from the charge/discharge behavior according to the cycle according to the comparative example it can be estimated that the electrolyte is sufficiently impregnated into the negative electrode after two cycles in which all the capacities are expressed.
- the battery After storing the half cell of the manufacturing example at room temperature for 3 hours, the battery was charged under 0.1 C c-rate condition, and the charged coin half cell was discharged under 0.1 C c-rate condition in one cycle. And the cycle of charge/discharge was repeated 5 times (voltage range: 0.005 V to 1 V).
- V t charge/discharge profile of the battery cell at time t
- V t-1 Charge/discharge profile of the battery cell 1 unit time before time t
- FIG. 3 is a graph showing the differential capacity obtained by differentiating the charging profile (x-axis: capacity, y-axis: voltage) of each cycle with respect to the capacity.
- one cycle and two cycles differ in the position of the peak and the behavior of the graph. The same is true for two and three cycles.
- the graph's behavior is almost the same, so that the three differential capacity curves coincide, which means that after three cycles, all of the reactable lithium ions are intercalated within the negative electrode, leading to the situation that the behavior of the graph of the differential capacity due to intercalation becomes the same after 3 cycles.
- the time point when the electrolyte is sufficiently impregnated in the negative electrode of the half cell may be determined as the time after 3 cycles.
- the half cell was assembled in the same manner as in Preparation Example, and the electrolyte was injected and stored at room temperature for 3 days so that the electrolyte was sufficiently impregnated into the electrode. Thereafter, charging/discharging was repeated five times with respect to the half cell in which the electrolyte solution was sufficiently impregnated under the same conditions as in Example 1. Then, as in Example 1, the charge profile (x-axis: capacity, y-axis: voltage) for each cycle was differentiated with respect to the capacity to calculate the differential capacity (dV/dQ) curve.
- the differential capacity curves of three cycles determined to be sufficiently impregnated time points in Example 1 and the differential capacity curve of one cycle in the reference example are shown in FIG. 4 , respectively. Referring to FIG. 4 , it can be seen that these two differential capacity curves overlap each other.
- the differential capacity curve of one cycle of the half cell of the reference example may be regarded as the differential capacity curve of the negative electrode sufficiently impregnated with the electrolyte. Therefore, the point that the three cycles of the differential capacity curve in Example 1 coincides with the one cycle of the differential capacity curve in Reference Example may mean that the result according to the determination method of the electrolyte solution impregnation time point of Example 1 is consistent with the fact.
- the method for analyzing the degree of impregnation of the electrolyte solution of the present invention may be evaluated as providing a reliable result in determining at what time point the electrolyte is sufficiently impregnated.
- a full-cell was assembled as follows, and a differential capacity curve for each cycle according to charge/discharge was produced.
- a membrane of porous polyethylene was interposed between the positive electrode and the negative electrode of the preparation example, and 0.5 wt % vinylene carbonate and 1 M LiPF 6 dissolved electrolyte were injected into a mixed solution of ethyl methyl carbonate (EMC) and ethylene carbonate (EC) with a volume ratio of 7:3, to thereby prepare a full cell. Thereafter, the full cell was stored at room temperature for 3 hours to wet the electrolyte solution.
- EMC ethyl methyl carbonate
- EC ethylene carbonate
- the analysis method of the present invention may be used to determine in which cycle the electrolyte is sufficiently impregnated.
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Abstract
Description
dV/dQ=(V t −V t-1)/(Q t −Q t-1) [Formula 1]
dV/dQ=(V t −V t-1)/(Q t −Q t-1) [Formula 1]
Claims (10)
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PCT/KR2019/009808 WO2020032545A1 (en) | 2018-08-09 | 2019-08-06 | Method for precisely analyzing degree of impregnation of electrolyte of electrode in cell |
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KR20210003600A (en) * | 2019-07-02 | 2021-01-12 | 주식회사 엘지화학 | Method for determining the degree of wetting using low current test |
KR102596153B1 (en) * | 2020-08-14 | 2023-10-30 | 주식회사 엘지에너지솔루션 | Apparatus and method for managing battery |
KR20220031412A (en) * | 2020-09-04 | 2022-03-11 | 주식회사 엘지에너지솔루션 | Apparatus and method for managing battery |
JP7208272B2 (en) * | 2021-01-08 | 2023-01-18 | プライムプラネットエナジー&ソリューションズ株式会社 | Controller and its use |
KR20220107550A (en) * | 2021-01-25 | 2022-08-02 | 주식회사 엘지에너지솔루션 | Apparatus and method for classifying battery |
CN113991198A (en) * | 2021-09-29 | 2022-01-28 | 江苏中兴派能电池有限公司 | Lithium ion battery electrolyte infiltration detection method |
CN115097341B (en) * | 2022-06-20 | 2023-04-07 | 楚能新能源股份有限公司 | Method for detecting lithium separation performance of graphite material |
WO2024136557A1 (en) * | 2022-12-23 | 2024-06-27 | 주식회사 엘지에너지솔루션 | Method for manufacturing lithium secondary battery |
WO2024145828A1 (en) * | 2023-01-04 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Electrolyte abnormality detection method and apparatus, electronic device, storage medium, and program product |
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CN111418107B (en) | 2023-08-25 |
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